CN101189187B - Mesostructured materials with high aluminum content - Google Patents
Mesostructured materials with high aluminum content Download PDFInfo
- Publication number
- CN101189187B CN101189187B CN2006800192931A CN200680019293A CN101189187B CN 101189187 B CN101189187 B CN 101189187B CN 2006800192931 A CN2006800192931 A CN 2006800192931A CN 200680019293 A CN200680019293 A CN 200680019293A CN 101189187 B CN101189187 B CN 101189187B
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- Prior art keywords
- central hole
- hole structure
- zeolite
- matrix
- nanocrystal
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 203
- 229910052782 aluminium Inorganic materials 0.000 title claims description 49
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 48
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 181
- 239000010457 zeolite Substances 0.000 claims abstract description 159
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 155
- 239000011159 matrix material Substances 0.000 claims abstract description 83
- 238000002360 preparation method Methods 0.000 claims abstract description 76
- 239000002159 nanocrystal Substances 0.000 claims abstract description 75
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 39
- 239000012798 spherical particle Substances 0.000 claims abstract description 23
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 54
- 238000002156 mixing Methods 0.000 claims description 52
- 239000002243 precursor Substances 0.000 claims description 49
- 239000013543 active substance Substances 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 239000004411 aluminium Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- 239000000443 aerosol Substances 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 15
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 13
- 239000007921 spray Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 230000003098 cholesteric effect Effects 0.000 claims description 4
- 239000002594 sorbent Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 31
- 229910000323 aluminium silicate Inorganic materials 0.000 description 28
- 238000005516 engineering process Methods 0.000 description 28
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 229920001577 copolymer Polymers 0.000 description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 238000000207 volumetry Methods 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 230000000875 corresponding effect Effects 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- 238000001338 self-assembly Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000012159 carrier gas Substances 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000004479 aerosol dispenser Substances 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000011805 ball Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 229910001657 ferrierite group Inorganic materials 0.000 description 3
- 229910052733 gallium Chemical group 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052680 mordenite Inorganic materials 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 229920001983 poloxamer Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- 229920000428 triblock copolymer Polymers 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- -1 and in this case Chemical compound 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910001423 beryllium ion Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003791 organic solvent mixture Substances 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000012976 tarts Nutrition 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229920002359 Tetronic® Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000012687 aluminium precursor Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001723 mesolite Inorganic materials 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000012686 silicon precursor Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003046 tetrablock copolymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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Abstract
The invention relates to a mesostructured material consisting of at least two essentially spherical particles, each particle comprising a mesostructured matrix based on alumina, said matrix having a pore size of 1.5-30nm and an alumina content of more than 46 wt% of the matrix and having amorphous walls with a thickness of 1-20nm, wherein the essentially spherical particles have a maximum diameter of 10 [ mu ] m. The mesostructured matrix may also contain silicon oxide. Each spherical particle of the mesostructured material may also contain zeolite nanocrystals, thereby forming a material having mixed pores of mesostructured and zeotype pores. The invention also relates to a preparation method of the material.
Description
Technical field
The present invention relates to field based on the central hole structure formed material of aluminum oxide.The invention still further relates to classification that has in microporosity and mesoporosity scope or the central hole structure formed material field of mixing the high aluminium content of hole.The invention still further relates to these preparation methods that so-called by using " aerosol " synthetic technology obtains.
Background technology
Since middle 1990s, academia has researched and developed new synthesis strategy widely, so that can be by having classification or mixing porosity (promptly, hole with several sizes) material obtains to have the material of the clear and definite porosity in the scope of non-constant width, that is, (G.J.of A.A.Soler-Illia, C.Sanchez from the poromerics to the large pore material, B.Lebeau, J.Patarin, Chem.Rev., 2002,102,4093).Obtained the controlled material in aperture.Especially, the coexistence in the aqueous solution or polar solvent by inorganic precursor and structurising agent (normally molecule or supramolecule ion or neutral surface active agent), so-called " fine chemistry " synthetic method has produced low temperature central hole structureization (mesostructured) material.By the monitoring electrostatic interaction or according to inorganic precursor relevant and the hydrogen bond between the structurising agent with the hydrolyzing reaction of inorganic precursor, can coordinated groups adorn organic phase, be formed on the micellar aggregates of tensio-active agent monitored, uniform-dimension in the inorganic matrix with mutually inorganic.Especially this collaborative self-assembly phenomenon of controlling by the concentration of structurising agent can be brought out by evaporating reagent solution gradually, the structurising agent concentration great majority of this reagent solution are usually less than micelle-forming concentration, the formation that this under sedimentary situation on the base material (" dip-coating " technology) causes the formation of central hole structure film or cause the central hole structure powder at spray solution (aerosol technology) afterwards.For example, patent US6,387, the 453 open methods that form central hole structure organic and inorganic hybrid films by " dip-coating " technology, thus, identical contriver uses aerosol technology to develop central hole structureization, pure silicon material (C.J.Brinker, Y.Lu in addition, A.Sellinger, H.Fan, Adv.Mater., 1999,11,7).Discharge hole by eliminating tensio-active agent then.Tensio-active agent is eliminated with chemical extraction method or thermal treatment usually.Based on the character of employed inorganic precursor and structurising agent and the operational condition of employing, the family that has developed several central hole structure formed materials.For example, broad research at first research and develop by Mobil, (the J.S.Beck of M41S family that forms by mesopore material, J.C.Vartuli, W.J.Roth, M.E. Leonowlez, C.T.Kresge, K.D.Schmitt, C.T.-W.Chu, D.H.Olson, E.W.Sheppard, S.B.McCullen, J.B.Higgins, J.L.Schlenker, J.Am.Chem.Soc., 1992,114,27,10834), this mesopore material has common sexangle by use, cubes or lamellar structure, 1.5-10nm the hole of uniform-dimension and the ionic surface active agent such as the quaternary ammonium salt of the amorphous wall that thickness is about 1-2nm obtain.Afterwards, in order to improve the performance of hydrothermal stability, the exploitation acid-alkaline relevant with these materials especially considered by directly synthesizing or synthesize back method aluminium element to be incorporated in the amorphous silicon skeleton simultaneously, and wherein the aluminosilicate material that is obtained has the Si/Al mol ratio (S.Kawi of 1-1000, S.C.Shen, Stud.Surf.Sci.Catal,, 2000,129,227; S.Kawi, S.C.Shen, Stud.Surf.Sci.Catal., 2000,129,219; R.Mokaya, W.Jones, Chem.Commun..1997,2185).Yet hydrothermal stability and the acid-alkaline that produces with these aluminosilicates do not allow them to be used for refining or petroleum chemistry method in the industrial age like this, this causes using the amphiphilic macromolecular of new texture agent such as segmented copolymer class gradually, and the latter has obtained to have the hole of uniform-dimension of common sexangle, sexangle, cubes or lamellar structure, 4-50nm and the central hole structure formed material of the amorphous wall that thickness is 3-7nm.Based on final central hole structure formed material required structure and tissue (organization) degree, employed synthetic method can be carried out in acid medium (pH≤1) (WO 99/37705) or neutral medium (WO96/39357), and wherein the character of employed structurising agent also has main effect.The central hole structure aluminosilicate material of Huo Deing has the hydrothermal stability of raising with respect to their other structurising agent synthetic homologue of usefulness like this, and their acid-alkaline keeps similar (1＜Si/Al＜1000).Yet low Si/Al molar ratio such as Si/Al＜20 are difficult to obtain, because be not easy a large amount of aluminium is incorporated into (D.Zhao in the material with these particular methods of operation, J.Feng, Q.Huo, N.Melosh, G.H.Fredrickson, B.F.Chmelka, G.D.Stucky, Science, 1998,279,548; Y.-H.Yue, A.G é d é on, J.-L.Bonardet, J.B.d ' Espinose, N.Melosh, J.Fraissard, Stud.Surf.Sci.Catal., 2000,129,209).
In addition, for the aluminosilicate material of the advantage that obtains to have simultaneously orderly central hole structure and crystallite network and do a lot of work.Several synthetic technologys that to develop mixing or compound central hole structure/zeolitic material have been put down in writing in the open source literature.First kind of synthetic technology comprise according to above-mentioned usual way in synthetic central hole structure aluminosilicate material of fs, then subordinate phase be generally used for the synthetic zeolite material structurising agent flood this material.The hydrothermal treatment consists that is fit to causes the zeolitization (US6 669 924) of the amorphous wall of initial central hole structure aluminosilicate.Second kind of synthetic technology comprises to be put into the colloidal solution of zeolite nuclear in the fouling agent of the central hole structureization that is generally used for producing final material.Generation and zeolite nuclear with inorganic matrix of orderly mesoporosity are simultaneously in this intramatrical increase, thereby obtain to have central hole structure aluminosilicate material (Z.Zhang, the Y.Ran of crystallization wall, F.Xiao, S.Qiu, L.Zhu, R.Wang, Y.Yu, Z.Zhang, B.Zou, Y.Wang, H.Sun, D.Zhao, Y.Wei, J.Am.Chem.Soc., 2001,123,5014; Y.Liu, W.Zhang, T.J.Pinnavaia, J.Am.Chem, Soc..2000,122,8791).A modification of these two kinds of technology at first is to prepare the mixture of aluminium and silicon precursor in the presence of two kinds of structurising agents, a kind of structurising agent can produce the zeolite system, and another kind can produce central hole structureization.This solution is then with carrying out two crystallisation stages under the variable hydrothermal treatment consists condition, fs forms the central hole structure with orderly hole, subordinate phase obtains the zeolitization (A.Karisson of amorphous wall, M.Stocker, R.Schmidt, Micropor.Mesopor.Mater., 1999,27,181).Not fully under the situation of control, these synthetic methods have the central hole structure of destruction and therefore lose the defective of the advantage of central hole structure, thereby make that the enforcement of these technology is very thorny at the zeolitization of the growth of zeolite nuclear or wall.Can avoid this phenomenon by direct formation central hole structure/Zeolite composite materials.Mixture (P.Prokesova, S.Mintova, the J.Cejka of the solution that this can be by thermal treatment zeolite nuclear and the solution of central hole structure manosil AS salt core, T.Bein, Micropor.Mesopor.Mater., 2003,64,165) or by growth zeolite layer on the surface of pre-synthetic central hole structure aluminosilicate finish (D.T.On, S.Kaliaguine, Angew.Chem.Iht.Ed., 2002,41,1036).Viewpoint from experiment, do not resemble above-mentioned " dip-coating " or " aerosol " technology fully, aluminosilicate with classification porosity of determining like this is not to obtain by inorganic precursor and structurising agent in the concentrated solution gradually, but usually the micelle-forming concentration value by the control texture agent in the aqueous solution or polar solvent directly precipitation obtain.In addition, the synthetic aging step that need be in autoclave of these materials that obtain by precipitation, and all reagent in product not with the stoichiometry combination, because they may be present in the upper strata.Usually the ultimate particle that obtains does not have uniform shapes, and general feature is that granularity is 200-500nm, and is bigger sometimes.
General introduction
The present invention relates to the central hole structure formed material formed by at least two kinds of substantially spherical particles, described each particle comprises the central hole structure matrix based on aluminum oxide, described matrix has the aperture of 1.5-30nm and accounts for the above alumina content of 46wt% of described matrix, and having thickness is the amorphous wall of 1-30nm, and wherein said substantially spherical particle has the maximum diameter of 10 μ m.Described central hole structure matrix optimization based on aluminum oxide comprises that ratio makes the Si/Al mol ratio strictness of described matrix less than 1 silicon oxide.
Described each substantially spherical particle can also comprise that the aperture is the zeolite nanocrystal of 0.2-2nm, makes described material according to the invention have the mixing hole of central hole structure and zeolite character simultaneously.
The invention still further relates to the preparation method of material according to the invention.Preparation comprises according to the method for central hole structure formed material of the present invention: a) mix at least a tensio-active agent, at least a aluminum precursor and optional at least a silica precursor in solution; B) solution that obtains in the step a) is carried out aerosol spray, form the spherical droplets that diameter is less than or equal to 200 μ m; C) dry described drop; And d) removes described tensio-active agent, obtain the central hole structure formed material.Preparation about central hole structure/zeolite mixing material, for example, at first begin preliminary step a0), the down synthetic maximum nano-scale of existence that is included at least a structurising agent equals the zeolite nanocrystal of 300nm, be scattered in wherein colloidal solution so that obtain described nanocrystal, perhaps can will have the zeolite crystal that the form that equals the nanocrystal of 300nm with maximum nano-scale is scattered in the characteristic in the solution and be incorporated in this mixture according to step a).The ordered structure of the matrix of each spheroidal particle of formation material according to the invention originates from the evaporation micellization or the self-assembly phenomenon of being brought out by so-called aerosol technology.
Advantage
The material that central hole structure formed material according to the present invention is made up of the substantially spherical particle, described each particle comprises the central hole structure matrix with high aluminium content.Described central hole structure matrix can also contain silicon oxide, and in this case, silicon oxide provides favourable acid-alkaline for material according to the invention.The present invention also provides has the material that mixes hole, its mesolite nanocrystal is held back in central hole structure matrix, this material is favourable, because it has zeolite family and simultaneously based on the material of aluminum oxide, the more specifically peculiar structure of central hole structure aluminosilicate material, structure and acid-alkaline.The ordered structure that originates from the material according to the invention of the evaporation micellization that brought out by so-called aerosol technology or self-assembly makes and can be easy to generate the central hole structure formed material that exists or do not have the zeolite nanocrystal, and neither destroy the character of central hole structure phase, do not destroy the character of the optional zeolite facies that exist yet, and can be fit to use, no matter their initial synthetic method how with various zeolite nanocrystals.In fact, has central hole structure in order to prepare/material of zeolite mixing hole, can adopt the zeolite crystal of size much larger than 300nm, because they have in solution, especially in acidic solution, more preferably in acid aqueous organopolysiloxane, equal the form dispersive performance of the nanocrystal of 300nm with maximum nano-scale.In addition, the generation of nano level central hole structure/zeolitic material has caused micropore and preferred be connected of araea porosae mesonoticae in same spheroidal particle.
In addition, with (promptly with non-homogeneous shape, irregular) compare much larger than the material of from prior art, learning of the form existence of the ultimate particle of 500nm with granularity, (diameter of these particles advantageously is that 50nm is to 10 μ m by spherical ultimate particle, preferred 50nm is to 300nm, the limited granularity of these particles and their uniform shape) form, existence or do not exist the central hole structure formed material according to the present invention of zeolite nanocrystal to make reagent and reaction product when material according to the invention is used for potential application, spread better.
In addition, known synthesis method with respect to the central hole structure formed material, material according to the invention prepares continuously, preparation time reduces (several hours, and be 12-24 hour when using high pressure), the stoichiometry that is present in the non-volatile group in the initial soln of reagent is maintained in material of the present invention.
Disclosure of the Invention
The objective of the invention is the central hole structure formed material formed by at least two kinds of substantially spherical particles, described each particle comprises the central hole structure matrix based on aluminum oxide, this matrix has the aperture of 1.5-30nm and accounts for the above alumina content of 46wt% of described matrix, this matrix has the amorphous wall that thickness is 1-30nm, and described substantially spherical particle has the maximum diameter of 10 μ m.
In the present invention, the central hole structure formed material is defined as having at least the material of orderly porosity of the mesoporosity yardstick of described each spheroidal particle, and promptly the hole by the uniform-dimension with 1.5-30nm and preferred 1.5-10nm is the yardstick ordering and porosity that be evenly distributed on (central hole structureization of material) in described each spheroidal particle.More particularly, within the scope of the invention, the central hole structureization of material is relevant with the matrix that comprises in described material; The matrix based on aluminum oxide that is included in described each spheroidal particle that constitutes material according to the invention is central hole structureization.It has the mesoporosity of the uniform-dimension of the 1.5-30nm that is evenly distributed in described each particle and preferred 1.5-10nm.Should be noted that, can also form the porosity of micropore character with the overlapping of the organic and inorganic inorganic wall at the interface that in the central hole structure process of the inorganic component of described material according to the invention, produces by the tensio-active agent that in the preparation process of material according to the invention, uses.Material between the mesoporosity of central hole structure matrix is unbodied, and having formed thickness is the wall of 1-30nm.The thickness of wall is corresponding to the spacing of separating a hole and another hole.The ordering of above-mentioned mesoporosity has caused the structurizing based on the matrix of aluminum oxide, and it can be sexangle, vermiform, cholesteric, lamelliform, co-continuous or cubical, is preferably vermiform.Material according to the invention can also have constructs macropore between particle.
According to the present invention, the described substantially spherical particle that constitutes material according to the invention has the maximum diameter of 10 μ m, it advantageously be 50nm to 10 μ m, more advantageously arrive 300nm for 50nm.More particularly, described particle is present in the material according to the invention with the form of aggregate.
Material according to the invention advantageously has 100-1200m
2/ g, more advantageously 200-800m
2/ g, also 200-600m more advantageously
2The specific surface area of/g.
First embodiment of material according to the invention all is an aluminium based on the central hole structure matrix of aluminum oxide.
Second embodiment of material according to the invention also comprises silicon oxide based on the central hole structure matrix of aluminum oxide.The matrix that is included in each spheroidal particle of material according to the invention is aluminosilicate in this case.Silica content in the alumo silicate matrix should make the strictness of Si/Al mol ratio less than 1.
The 3rd embodiment of material according to the invention, described each spheroidal particle comprise that also the aperture is the zeolite nanocrystal of 0.2-2nm.With described spheroidal particle is yardstick, material according to the invention so not only have 1.5-30nm and preferred 1.5-10nm uniform-dimension the mesoporosity yardstick, be uniformly distributed in the ordering porosity (aforesaid central hole structureization) in described each particle, and has a zeolite type microporosity, its characteristic (structure type of zeolite, the chemical constitution of zeolite framework) is with the basis that is chosen as of zeolite nanocrystal.The 3rd embodiment of material according to the invention, the zeolite nanocrystal has 0.2-2nm, preferred 0.2-1nm, the more preferably aperture of 0.2-0.6nm.Described nanocrystal has produced the microporosity in each the substantially spherical particle that constitutes material according to the invention.The 3rd embodiment of material according to the invention, described matrix can all be that silicon maybe can also comprise silicon oxide.In following specification sheets, be called as central hole structure/zeolite mixing material according to the material of the 3rd embodiment.
According to the 3rd embodiment of central hole structure formed material of the present invention, the zeolite nanocrystal advantageously accounts for the 0.1-30wt% of material of the present invention, preferred 0.1-20wt%, more preferably 0.1-10wt%.Any zeolite, especially with non-limiting way at " Atlas of Zeolite FrameworkTypes; " the 5th revised edition, 2001, Ch.Baerlocher, W.M.Meier, those that enumerate among the D.H.Olson can be used for being present in the zeolite nanocrystal of each the substantially spherical particle that constitutes material according to the invention.The zeolite nanocrystal preferably includes at least a zeolite ZSM-5, ZSM-48, ZSM-22, the ZSM-23 of being selected from, ZBM-30, EU-2, EU-11, silicite, β, zeolite A, faujusite, Y, USY, VUSY, SDUSY, mordenite, NU-87, NU-88, NU-86, NU-85, IM-5, IM-12, the zeolite among ferrierite and the EU-1.More preferably, the zeolite nanocrystal comprises the zeolite at least a MFI of being selected from, BEA, FAU and the LTA structure-type zeolite.Different zeolites, especially the nanocrystal of different structure type zeolite can be present in each spheroidal particle that constitutes material according to the invention.Especially, each spheroidal particle that constitutes material according to the invention can advantageously comprise at least the first kind of zeolite nanocrystal and at least the second kind of zeolite nanocrystal, and the zeolite of described first kind of zeolite nanocrystal is selected from zeolite ZSM-5, ZSM-48, ZSM-22, ZSM-23, ZBM-30, EU-2, EU-11, silicite, β, zeolite A, faujusite, Y, USY, VUSY, SDUSY, mordenite, NU-87, NU-88, NU-86, NU-85, IM-5, IM-12, ferrierite and EU-1 preferentially are selected from MFI, BEA, the zeolite of FAU and LTA structure-type, the zeolite of second kind of zeolite nanocrystal is different from the zeolite of described first kind of zeolite nanocrystal, and is selected from zeolite ZSM-5, ZSM-48, ZSM-22, ZSM-23, ZBM-30, EU-2, EU-11, silicite, β, zeolite A, faujusite, Y, USY, VUSY, SDUSY, mordenite, NU-87, NU-88, NU-86, NU-85, IM-5, IM-12, ferrierite and EU-1 preferentially are selected from MFI, BEA, the zeolite of FAU and LTA structure-type.The zeolite nanocrystal advantageously comprises at least a zeolite that is entirely silica or also contains at least a element T except silicon, and described element T is selected from aluminium, iron, boron, indium and gallium, preferred aluminium.The zeolite nanocrystal has the maximum particle size of 300nm, preferably has the granularity of 30-200nm.
Have full aluminium type central hole structure matrix or belong to aluminosilicate character and choose the central hole structure formed material of the present invention with zeolite nanocrystal of holding back wantonly in this matrix and can obtain with the form of powder, ball, ball, particle or extrudate, wherein forming operation adopts standard technique well known by persons skilled in the art.Material according to the invention preferably obtains with powder type, and this powder is that the substantially spherical particle of 10 μ m is formed by maximum diameter, and this helps may spreading of compound under the situation that material according to the invention is used in potential industrial application.
Purpose of the present invention still prepares the method for material according to the invention.At first, provide preparation to comprise the method according to central hole structure formed material of the present invention of the matrix of full aluminium type central hole structure matrix or aluminosilicate character.Described method comprises: a) mix at least a tensio-active agent, at least a aluminum precursor and optional at least a silica precursor in solution; B) solution that obtains in the step a) is carried out aerosol spray, form the spherical droplets that diameter is less than or equal to 200 μ m; C) dry described drop; And d) removes described tensio-active agent, obtain the central hole structure formed material.In following specification sheets, described method is called as " according to main preparation methods of the present invention ".
Aluminum precursor that uses in the step a) according to main preparation methods of the present invention and optional silica precursor are to well known to a person skilled in the art precursors of inorganic oxides.Aluminum precursor is formula AlX advantageously
3Inorganic aluminate, wherein X is halogen or group NO
3X is chlorine preferably.Can also use Tai-Ace S 150 Al
2(SO
4)
3As inorganic salt.Aluminum precursor can also be formula Al (OR ")
3Organometallic precursor, R wherein "=ethyl, sec.-propyl, normal-butyl, sec-butyl or the tertiary butyl, or chelating precursor is as Acetyl Acetone aluminium (Al (C
5H
8O
2)
3).Aluminum precursor can also be the oxide compound or the oxyhydroxide of aluminium.If be present in the step a), silica precursor is so by any silica source, advantageously by formula SiO
2, the water glass precursor of NaOH, formula SiCl
4Chlorination precursor, formula Si (OR)
4Organometallic precursor (wherein R=H, methyl or ethyl) or formula Si (OR)
4-xCl
xChlorination alkoxide precursor (wherein R=H, methyl or ethyl, x are 0-4) obtain.Silica precursor is formula Si (OR) advantageously
4-xR '
xOrganometallic precursor, R=H wherein, methyl or ethyl, R ' they are alkyl chain or functionalised alkyl chain, for example mercaptan, amino, beta-diketon or sulfonic acid group functionalised alkyl chain, wherein x is 0-4.
The tensio-active agent that is used to prepare according to the mixture of the step a) of main preparation methods of the present invention is ion or nonionogenic tenside or the mixture of the two.This ionic surface active agent preferentially is selected from
Or ammonium ion, more preferably be selected from quaternary ammonium salt, for example hexadecyl trimethylammonium bromide (CTAB).This nonionogenic tenside preferably can be to have at least two opposed polarity parts to give their multipolymers of amphiphilic macromolecular performance.It especially can be the multipolymer that is selected from the non exhaustive list of following multipolymer family: fluorinated copolymers ([CH
2-CH
2-CH
2-CH
2-O-CO-R1]-, R1=C wherein
4F
9, C
8F
17Deng), bioabsorbable copolymer, for example poly-acid of amine (poly--Methionin, alginates etc.), tree-shaped polymkeric substance, segmented copolymer and any other well known by persons skilled in the art be made up of poly-(alkylidene oxide) chain have amphipathic multipolymer (S.F
Rster, M.Antionnettl, Adv.Mater., 1998,10,195-217, S.F
Rster, T.P1antenberg, Angew.Chem.Int.Ed., 2002,41,688-714, H.C
Lfen, Macromol.Rapid Commun, 2001,22,219-252).Within the scope of the invention, the multipolymer that is selected from the segmented copolymer family that is made up of poly-(alkylidene oxide) chain is preferred the use.Described segmented copolymer preferably has the segmented copolymer of two, three or four blocks, and each block is made up of poly-(alkylidene oxide) chain.For diblock copolymer, one of block is made up of hydrophilic poly-(alkylidene oxide) chain, and another block is made up of hydrophobic poly-(alkylidene oxide) chain.For triblock copolymer, two blocks are made up of hydrophilic poly-(alkylidene oxide) chain, and another block is made up of hydrophobic poly-(alkylidene oxide) chain between the block of two possess hydrophilic property parts.Under the situation of triblock copolymer, preferably poly-(ethylene oxide) chain of hydrophilic poly-(alkylidene oxide) chain is expressed as (PEO)
x(PEO)
z, hydrophobic poly-(alkylidene oxide) chain is poly-(propylene oxide) chain, is expressed as (PPO)
y, poly-(oxybutylene) chain or each bar chain are the combination chain of the monomeric mixture of several oxyalkylenes.More preferably, under the situation of triblock copolymer, use formula (PEO)
x-(PPO)
y-(PEO)
zCompound, wherein x is 5-300, y is 33-300, z is 5-300.The value of x and z is preferably identical.More advantageously, use the wherein compound of x=20, y=70 and z=20 (poly-(ethylene oxide)
20-poly-(propylene oxide)
70-poly-(ethylene oxide)
20, or be called P123) and the compound (F127) of x=106, y=70 and z=106 wherein.Can be called the commodity nonionogenic tenside of Pluronic (BASF), Tetronic (BASF), Triton (Sigma), Tergitol (Union Carbide) and Brij (Aldrich) as the nonionogenic tenside in the preparation method's of the present invention step a) by commodity in use.For Tetrablock copolymer, two blocks are made up of hydrophilic poly-(alkylidene oxide) chain, and two blocks are made up of hydrophobic poly-(alkylidene oxide) chain in addition.
Produced diameter according to the step of the spray mixing thing of the step b) of main preparation methods of the present invention and be less than or equal to 200 μ m, preferred 50nm is to the spherical droplets of 20 μ m.The distribution of sizes of these drops is lognormalitys.Aerosol dispenser used herein is the 3078 type industrial equipmentss that TSI provides.Solution be sprayed at delivery of carrier gas O
2/ N
2Carry out under the pressure P that equals 1.5 crust the indoor of mixture (dry air).According to the step c) of main preparation methods of the present invention, begin dry described drop.This drying is by using carrier gas O
2/ N
2Mixture carries described drop to carry out in Glass tubing, and this causes as this specification sheets solution hereinafter described such as the evaporation gradually of acid aqueous organopolysiloxane, therefore obtains spherical ultimate particle.This drying is undertaken by described particle being sent in the stove that temperature can regulate ideally, and common temperature range is 50-600 ℃, and preferred 80-400 ℃, wherein the residence time of these particles in stove is about 1 second.Use the strainer collecting granules then, form according to central hole structure formed material of the present invention.The pump of being located at the loop end promotes residue is sent in the aerosol experimental installation.According to the drying of the drop of the step c) of main preparation methods of the present invention advantageously succeeded by in temperature 50-150 ℃ baking oven, passing through.In order to obtain material according to the invention, according to the elimination of tensio-active agent in the step d) of main preparation methods of the present invention advantageously by chemical extraction method or by thermal treatment, preferably pass through at 300-1000 ℃, more specifically calcined 1-24 hour in the air in 500-600 ℃ the temperature range, finished in preferred 2-6 hour.
The present invention also provides and has been used for preparation according to central hole structure of the present invention/zeolite mixing material, that is, each spheroidal particle that constitutes this material comprises two kinds of alternative methods of the material of the central hole structure matrix of full aluminium type or aluminosilicate character and the zeolite nanocrystal that the aperture is 0.2-2nm.
First embodiment of method of the material of zeolite nanocrystal is held back in preparation according to the present invention in the central hole structure matrix of oxide, hereinafter referred to as " according to the first method of preparation central hole structure of the present invention/zeolite mixing material ", comprise the above-mentioned central hole structure formed material that is used to prepare matrix with full aluminium type central hole structure matrix or aluminosilicate character, according to the same steps as of main preparation methods of the present invention a), b), c) and d).Described first method according to preparation central hole structure of the present invention/zeolite mixing material also comprises preliminary step a
0), the down synthetic maximum nano-scale of existence that is included in structurising agent equals the zeolite nanocrystal of 300nm, is scattered in wherein colloidal solution to obtain described nanocrystal.According to a
0) the described colloidal solution that obtains is incorporated in the mixture according to the step a) of main preparation methods of the present invention.Therefore described first method according to preparation central hole structure of the present invention/zeolite mixing material comprises: a
0) synthetic maximum nano-scale equals the zeolite nanocrystal of 300nm in the presence of at least a structurising agent, is scattered in wherein colloidal solution to obtain described nanocrystal; A ') in solution, mixes at least a tensio-active agent, at least a aluminum precursor, optional at least a silica precursor and at least a according to a
0) colloidal solution that obtains; B ') with step a ') in the solution that obtains carry out aerosol spray, form the spherical droplets that diameter is less than or equal to 200 μ m; C ') dry described drop; And d ') removes described tensio-active agent and described structurising agent, obtain central hole structure/zeolite mixing material.
Step a according to the first method of preparation central hole structure of the present invention/zeolite mixing material
0), come the synthetic zeolite nanocrystal according to schedule of operation well known by persons skilled in the art.Especially, people such as T.Bein, Micropor.Mesopor.Mater., 2003,64,165 have described the synthetic of beta-zeolite nanocrystal.T.J, people such as Pinnavaia, J.Am.Chem.Soc., 2000,122,8791 have described the synthetic of Y zeolite nanocrystal.People such as Kloetstra, Microporous Mater., 1996,6,287 have described the synthetic of octahedra zeolite nanocrystal.Several pieces of publications have been described the synthetic of ZSM-5 zeolite nanocrystal: people such as R.de Ruiter, Synthesis of Microporous Materials, Vol.I; M.L.Occelli, H.E.Robson (eds.), Van Nostrand Reinhold, NewYork, 1992,167; A.E.Persson, B.J.Schoeman, J.Sterte, J.-E.Otterstedt, Zeolites, 1995,15,611-619.Generally, the zeolite nanocrystal contains at least a silica source, the optional at least a at least a source that is selected from the element T in aluminium, iron, boron, indium and the gallium by preparation, and the reaction mixture of preferred at least a aluminium source and at least a structurising agent synthesizes.This reaction mixture is water-based or water-bearing organic, for example water-alcohol mixture.This reaction mixture advantageously is under the hydrothermal condition, under autogenous pressure, and the optional gas that adds, nitrogen for example at 50-200 ℃, under preferred 60-170 ℃ the temperature, also more preferably is being no more than under 120 ℃ the temperature, till forming the zeolite nanocrystal.When described hydrothermal treatment consists finishes, obtained colloidal solution, wherein nanocrystal is in dispersion state.According to want synthetic zeolite, structurising agent can be ion or neutral.Usually use the structurising agent of following non exhaustive list: nitrogenous organic cation, the element of basic metal family (Cs, K, Na etc.), ether ring, diamines and well known to a person skilled in the art any other structurising agent.
In second embodiment according to the method for preparing central hole structure/zeolite mixing material of the present invention, hereinafter referred to as " according to the second method of preparation central hole structure of the present invention/zeolite mixing material ", at first use and have the form that equals the nanocrystal of 300nm with maximum nano-scale and be scattered in the solution zeolite crystal of the characteristic in for example acid aqueous organopolysiloxane.Described zeolite crystal is incorporated into the mixture according to the step a) of main preparation methods of the present invention of the above-mentioned central hole structure formed material that is used for preparing the matrix with full aluminium type central hole structure matrix or aluminosilicate character.Described second method according to preparation central hole structure of the present invention/zeolite mixing material comprises: a ") in solution, mix at least a tensio-active agent, at least a aluminum precursor, optional at least a silica precursor and be scattered in zeolite crystal in the described solution with the form that maximum nano-scale equals the nanocrystal of 300nm; B ") with step a ") in the solution that obtains carry out aerosol spray, form the spherical droplets that diameter is less than or equal to 200 μ m; C ") dry described drop; And d ") remove described at least tensio-active agent to obtain central hole structure/zeolite mixing material.
Step a in the second method of preparation central hole structure according to the present invention/zeolite mixing material ") in, zeolite crystal adopted.Well known in the prior art, have in solution, for example in acid aqueous organopolysiloxane, equal any crystalline zeolite of form dispersive performance of the nanocrystal of 300nm, be suitable for implementation step a with maximum nano-scale ").Described zeolite crystal synthesizes by method known to those skilled in the art.Step a ") in the zeolite crystal that uses can be the form of nanocrystal.Be scattered in solution, aqueous organopolysiloxane for example, the granularity in the preferred acidic aqueous organopolysiloxane is greater than 300nm, and for example 300nm uses to the form that the zeolite crystal of 200 μ m also advantageously equals the nanocrystal of 300nm with maximum nano-scale.Functionalized by nanocrystal surface, it also is possible obtaining the nanocrystal form dispersive zeolite crystal that equals 300nm with maximum nano-scale.Employed zeolite crystal is their thick synthesized form,, still contains structurising agent that is, or is their calcinated form,, has removed the form of described structurising agent that is.When employed zeolite crystal was their thick synthesized form, described structurising agent was in the steps d of the second method of preparation central hole structure according to the present invention/zeolite mixing material method ") in eliminate.
According to two kinds of methods of preparation central hole structure of the present invention/zeolite mixing material, respectively at the step a ' of the first method of preparation central hole structure according to the present invention/zeolite mixing material) and according to the step a of the second method of preparation central hole structure of the present invention/zeolite mixing material ") in the aluminum precursor that uses and optional silica precursor be abovely in main preparation methods according to the present invention, to have given those of the central hole structure formed material of matrix of full aluminium type central hole structure matrix or aluminosilicate character for preparation.Respectively at the step a ' of the first method of preparation central hole structure according to the present invention/zeolite mixing material) and according to the step a of the second method of preparation central hole structure of the present invention/zeolite mixing material ") in the tensio-active agent that uses like this equally.It can be ion or nonionogenic tenside.The tensio-active agent of the segmented copolymer form of being made up of poly-(alkylidene oxide) chain is particularly preferred.The part of central hole structure formed material that has the matrix of full aluminium type central hole structure matrix or aluminosilicate character in above preparation according to main preparation methods of the present invention that specifies of this tensio-active agent form (provides in the step a).
Mix therein according to the step a) of main preparation methods of the present invention or according to the step a ' of the first method of preparation central hole structure of the present invention/zeolite mixing material) or according to the step a of the second method of preparation central hole structure of the present invention/zeolite mixing material ") the solution of all reagent can be acid, neutral or alkaline.Described solution is tart preferably, has to equal 3 the maximum pH of preferred 0-2.Being used to obtain the acid that the highest pH equals 3 acidic solution is hydrochloric acid, sulfuric acid and nitric acid without limitation.Described solution can be water-based, maybe can be water-ORGANIC SOLVENT MIXTURES, and this organic solvent is water-miscible polar solvent preferably, especially THF or alcohol, and under latter event, ethanol preferably.Described solution can also be organically basically, preferred alcohol basically, and wherein the amount of water should make the hydrolysis (stoichiometry) of guaranteeing inorganic precursor.More preferably, the described solution that mixes at least a aluminum precursor, at least a tensio-active agent and optional at least a silica precursor is acidic aqueous organic mixture, more preferably acid water-alcohol mixture.
Matrix in material according to the invention also contains under the preferable case of silicon oxide except aluminum oxide, according in the step a) of main preparation methods of the present invention or according to the step a ' and a of first and second kinds of methods of preparation central hole structure of the present invention/zeolite mixing material ") in silica and the concentration of aluminum precursor recently define with the Si/Al mole, this Si/Al mol ratio is strictly less than 1.In order to prepare according to central hole structure of the present invention/zeolite mixing material, step a ' in the first method of preparation central hole structure according to the present invention/zeolite mixing material) in the colloidal solution of introducing in the amount of dispersive zeolite nanocrystal and at the step a of the second method of preparation central hole structure according to the present invention/zeolite mixing material ") in the amount of the zeolite crystal introduced make the zeolite nanocrystal advantageously account for the 0.1-30wt% of central hole structure of the present invention/zeolite mixing material respectively; preferably 0.1-20wt%, more preferably 0.1-10wt%.Be incorporated into according to the step a) of main preparation methods of the present invention or according to the step a ' of the first method of preparation central hole structure of the present invention/zeolite mixing material) or according to the step a of the second method of preparation central hole structure of the present invention/zeolite mixing material ") mixture in the starting point concentration c of tensio-active agent
oDefine c
oAccording to well known to a person skilled in the art micelle-forming concentration (c
Mc) define.c
McBe peak concentration, surpass this concentration, the arrangement phenomenon certainly of surfactant molecule takes place in solution.Concentration c
oCan be lower than, be equal to or higher than c
McPreferably, it is lower than c
McIn three kinds of methods according to the present invention (according to main preparation methods of the present invention, according to the first method of preparation central hole structure of the present invention/zeolite mixing material with according to the second method of preparation central hole structure of the present invention/zeolite mixing material) each preferred implementation in, concentration c
oBe lower than c
Mc, according to three kinds of preparation methods' of the present invention each each step a), a ') and a ") described target solution be acid water-alcohol mixture.
In each each step a) according to three kinds of preparation methods of the present invention, a ') and a ") described target solution be water-ORGANIC SOLVENT MIXTURES and be preferably under the tart situation; preferably; in each each step a); a ' according to three kinds of preparation methods of the present invention) and a ") in, surfactant concentration subcritical micellar concentration when the central hole structure of matrix melts the beginning, make each each step b) according to three kinds of preparation methods of the present invention, b ') and b ") described in the aerosol technology evaporation passed through of aqueous organopolysiloxane (preferred acidic) brought out micellization or self-assembly phenomenon, caused the central hole structureization of the matrix of material according to the invention.Under the situation of preparation central hole structure/zeolite mixing material, the central hole structureization of the matrix of material is at the step b ' of the first method of preparation central hole structure according to the present invention/zeolite mixing material) and c ') in, or at the step b of the second method of preparation central hole structure according to the present invention/zeolite mixing material ") and c ") in, around the zeolite nanocrystal that shape and size remain unchanged, take place.Work as c
o＜c
McThe time, be that aluminum precursor, tensio-active agent and optional gradual the concentrating of silica precursor in each drop causes surfactant concentration c＞c up to the evaporation by this aqueous organopolysiloxane (preferred acidic) according to the present invention and according to the central hole structureization of the matrix of the material of one of three kinds of methods of the present invention preparations
McThe result.
Usually, the total concn increase of aluminum precursor, optional silica precursor and tensio-active agent causes the aluminum precursor of hydrolysis around self-organizing list's surface-active agent and the precipitation of optional silica precursor, thereby causes the structurizing of material according to the invention.By collaborative self-assembly mechanism, interaction mutually causes the aluminum precipitation of the hydrolysis around self-organizing list's surface-active agent and the condensation of optional hydrolysis silica precursor with organic/inorganic for inorganic/inorganic phase, organic/organic phase.Under the situation of preparation central hole structure/zeolite mixing material, in described self-assembly phenomenon process, hold back in the central hole structure matrix of the alumina base that the zeolite nanocrystal comprises in each the substantially spherical particle that constitutes material of the present invention.Aerosol technology is used to implement each step b), the b ' according to each of three kinds of preparation methods of the present invention) and b ") particularly advantageous; so that force the reagent that is present in the initial soln to interact; loss material is not possible; saved solvent; therefore initial all aluminium elements that exist, optional silicon and optional zeolite nanocrystal are preserved in all three kinds of methods according to the present invention fully, but not are removed in filtration that runs in standard synthetic method well known by persons skilled in the art and the washing step.
Step b ' according to the second method of the first method of preparation central hole structure of the present invention/zeolite mixing material or preparation central hole structure/zeolite mixing material), c ') and d ') or b "), c ") and d ") with step b), c according to main method of the present invention) and d) carry out under the identical operations condition.
Choose wantonly and contain the central hole structure formed material of the present invention of the zeolite nanocrystal of in central hole structure matrix, holding back by several analytical technologies, especially by small angle X-ray diffraction (little angle DRX), big angle X-ray diffraction (big angle DRX), nitrogen volumetry (BET), transmission electronic microscope checking (TEM), the plasma emission spectroscopy method (ICP) that scanning electronic microscope examination (SEM) and high frequency bring out characterizes.
Small angle X-ray diffraction technology (value of angle 2 θ is 0.5-6 °) can characterize the periodicity by the nanoscale that orderly mesoporosity produced of the central hole structure matrix of material of the present invention.In following specification sheets, by adopting copper radiation (wavelength 1.5406
), use by reflective operation and diffractometer that the rear portion monochromatic illuminator is housed powder is carried out X-ray analysis.Corresponding to set angle 2 θ values usually observed peak on the diffractogram and the net between apart from d
(hkl)Relevant, and distance is the feature ((hkl) is the Miller's indices of reciprocal networks) of the structural symmetry of the material represented with the Bragg equation formula: 2d between net
(hkl)* sin (θ)=η * λ.This indexing can be measured the mesh parameter (abc) of straight-forward network, wherein sexangle, cubes, cholesteric, lamelliform, co-continuous or the vermicular texture of the value of these parameters to be obtained then.For example, form by the substantially spherical particle that comprises alumo silicate matrix and according to main preparation methods of the present invention by using specific segmented copolymer poly-(ethylene oxide)
20-poly-(propylene oxide)
70-poly-(ethylene oxide)
20(PEO
20-PPO
70-PEO
20Or Pluronic 123) the small angle X-ray diffraction figure of the central hole structure formed material of Huo Deing has the relevant peaks of differentiating fully corresponding to the correlation distance between the hole, this is the feature of worm type structure, defines with Bragg equation formula 2d*sin (θ)=η * λ.
Big angle X-ray diffraction (value of angle 2 θ is 5-100 °) technology makes can characterize crystalline solid, and this crystalline solid defines by unit mode or the basic grid that repeats molecular scale.This technology is followed the physical principle identical with controlling the small angle X-ray diffraction technology.Therefore big angle DRX technology is used to analyze central hole structure/zeolite mixing material, because this technology extremely is suitable for being present in the structural characterization of formation according to the zeolite nanocrystal in each substantially spherical particle of central hole structure of the present invention/zeolite mixing material.Especially, this technology can obtain the aperture of zeolite nanocrystal.For example, the big angle of the central hole structure/zeolite mixing material that comprises ZSM-5 (MFI) type zeolite nanocrystal that obtains according to first or second method of preparation central hole structure of the present invention/zeolite mixing material has the diffractogram relevant with the symmetry group Pnma (No.62) of big angle ZSM-5 zeolite respectively with small angle X-ray diffraction figure and corresponding to the relevant little angular correlation peak of differentiating fully of worm type structure correlation distance d between hole and central hole structure matrix, wherein this central hole structure matrix is aluminosilicate character, gathers (ethylene oxide) by using specific segmented copolymer
106-poly-(propylene oxide)
70-poly-(ethylene oxide)
106(PEO
106-PPO
70-PEO
106Or F 127) obtains.The angle value that obtains with the RX diffractogram makes and can turn back to correlation distance d:2d*sin (θ)=η * λ according to Bragg's equation.The mesh parameter a that is used for the characterize nanocrystal, the b that is obtained well known to a person skilled in the art value consistent (" the Collection of Simulated XRD Powder Patterns for Zeolites that ZSM-5 (MFI) type zeolite nanocrystal obtains with c with usefulness; " the 4th revised edition, 2001, M.M.J.Treacy, J.B.Higgins).
The nitrogen volumetry is corresponding to passing through pressurize physical adsorption nitrogen molecule in the hole of material gradually under steady temperature, this provides about the information of the particular configuration characteristic of material according to the invention (aperture, porosity type, specific surface area).Especially, can obtain the specific surface area and the mesoporosity distribution of material.Specific surface area is defined as BET specific surface area (S
BET, m
2/ g), measure by nitrogen adsorption according to the ASTM D 3663-78 standard that " The Journal of American Society, " 60,309 (1938) described BRUNAUER-EMMETT-TELLER methods by magazine are set up.Void distribution has been represented the mesoporosity colony that concentrates on 1.5-50nm, measures by Barrett-Joyner-Halenda (BJH) model.Obtain like this " The Journal of American Society, " in 73,373 (1951) description is arranged, by E.P.Barrett, L.G.Joyner and P.P.Halenda write at magazine according to the absorption-desorption thermoisopleth of BJH model.In the following description, the mesoporosity diameter phi of set central hole structure matrix is corresponding to nitrogen adsorption method mean diameter, be defined as a kind of like this diameter, take 50% of volume of voids (Vp) that the absorption branch line of isothermal nitrogen line measures less than all holes of this diameter.In addition, the form of nitrogen adsorption isotherm and Narrow Hystersis can provide about the mesoporosity character and the main information that may exist of the relevant microporosity of the zeolite nanocrystal when being present in the central hole structure matrix of oxide.For example, according to of the present invention and according to main preparation methods of the present invention by using specific segmented copolymer poly-(ethylene oxide)
20-poly-(propylene oxide)
70-poly-(ethylene oxide)
20(PEO
20-PPO
70-PEO
20Or Pluronic123 or P123) nitrogen adsorption isotherm of the central hole structure aluminosilicate material that obtains as tensio-active agent characterizes with the adsorption isothermal line and the H1 type Narrow Hystersis of IV class, and the curve of the void distribution of being correlated with has been represented the mesoporosity colony of the uniform-dimension that concentrates on 4-10nm.For central hole structure/zeolite mixing material, the nitrogen adsorption isotherm of this material that comprises ZSM-5 (MFI) type zeolite nanocrystal that obtains according to first or second method of preparation central hole structure of the present invention/zeolite mixing material provides the distinctive I type of poromerics thermoisopleth for low P/PO value (wherein PO is the saturation vapour pressure of temperature T), and for high P/PO value, IV type thermoisopleth and H1 type Narrow Hystersis are provided, wherein this central hole structure matrix is aluminosilicate character, gathers (ethylene oxide) by using specific segmented copolymer
106-poly-(propylene oxide)
70-poly-(ethylene oxide)
106(PEO
106-PPO
70-PEO
106Or F 127) obtain, relevant hole distribution curve has been represented mesoporosity overall of the uniform-dimension that concentrates on 4-10nm.
About central hole structure matrix, difference between pore diameter φ that determines with above-mentioned little angle DRX and the value of mesh parameter a makes can acquisition amount e, e=a-φ wherein, its representative is at the thickness of the amorphous wall of the central hole structure matrix of the spheroidal particle that constitutes material according to the invention.Described mesh parameter a is related with interpore correlation distance d by the geometrical factor of geometry of representing this phase, for example, under the situation of sexangle grid, e=a-φ, wherein a=2*d/ √ 3, under the situation of worm type structure, e=d-φ.
Transmission electron microscope (TEM) analysis also is a technology that is widely used in the structure that characterizes these materials.TEM makes can form the solid image that will study, particulate structure organization, structure or form that the contrast that is wherein observed representative is observed, and the resolving power of this technology reaches maximum 0.2nm.In the following description, the TEM photo is taken in the section of sample, so that observe the section of the substantially spherical particle of material according to the invention.For example, have the substantially spherical particle of vermiform central hole structure with the TEM image that obtains by the central hole structure aluminosilicate material of using specific segmented copolymer Pluronic 123 to obtain according to main preparation methods of the present invention and according to the present invention, wherein this material defines with the dark space.
The analysis of image can also obtain the peculiar parameter d of above-mentioned central hole structure matrix, φ and e.For central hole structure/zeolite mixing material, the TEM image that this material that comprises ZSM-5 (MFI) type zeolite nanocrystal that obtains with first or second method of preparation central hole structure according to the present invention/zeolite mixing material obtains has vermiform central hole structure (wherein this material defines with the dark space) in same spheroidal particle, in this vermiform central hole structure, observed the opaque article of representing the zeolite nanocrystal of in central hole structure matrix, holding back, wherein this central hole structure matrix is aluminosilicate character, obtains by using specific segmented copolymer P123.The analysis of image can also obtain the peculiar parameter d of above-mentioned central hole structure matrix, φ and e, can also observe the netted plane of nanocrystal sometimes in this same block (block), but not more than the opaque article enumerated, therefore can obtain the structure of zeolite.
Form and size-grade distribution that the photo that obtains by analysis scanning electronic microscope inspection (SEM) has been established ultimate particle.
The structure of the central hole structure matrix of each particle of formation material according to the invention can be cubes, vermiform, cholesteric, lamelliform or co-continuous or hexagonal, depends on the character of selection as the tensio-active agent of structurising agent.It is vermicular texture preferably.
The present invention relates to the purposes that central hole structure formed material according to the present invention is used molecular sieve as the sorbent material or the separation of monitoring pollution.Therefore purpose of the present invention also comprises the sorbent material that contains with good grounds central hole structure formed material of the present invention.It also can be advantageously used for catalyzed chemical reaction, for example the acid solid of chemical reaction that takes place in refining and petroleum chemistry field of catalysis.
When central hole structure formed material according to the present invention was used as catalyzer, this material can combine with the inorganic matrix and the metallographic phase of inertia or catalytic activity.Inorganic matrix can be simply exists as the binding agent that the particle of catalyzer (extrudate, pellet, ball, the powder) material of different form known is gathered, perhaps can be used as thinner adds, so that the technology transformation efficiency is exerted one's influence, otherwise the fast speed of this technology ether is carried out, and causes break-up of catalyst owing to a large amount of coke form.Typical inorganic matrix is the catalyzer base material especially, for example various forms of silicas, aluminum oxide, silica-alumina, magnesium oxide, zirconium white, the oxide compound of titanium and boron, the phosphoric acid salt of aluminium, titanium and zirconium, clay, as kaolin, wilkinite, montmorillonite, sepiolite, attapulgite, Fuller's earth, poromerics, for example SiO
2-Al
2O
3, SiO
2-ZrO
2, SiO
2-ThO
2, SiO
2-BeO, SiO
2-TiO
2Or any binding substances of these compounds.Inorganic matrix can be an all cpds, especially inertia phase and active mixture mutually.Described material of the present invention can also combine with at least a zeolite, can play main mutually active or additive.Metallographic phase can be incorporated in the described material of the present invention.It can also by ion-exchange or be selected from the positively charged ion among following the oxide compound dipping is incorporated on the inorganic matrix or inorganic matrix-central hole structure solid unit on: Cu, Ag, Ga, Mg, Ca, Sr, Zn, Cd, B, Al, Sn, Pb, V, P, Sb, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Pt, Pd, Ru, Rh, Os, Ir and any other periodictable element.
The catalytic composition that comprises material of the present invention extensively is suitable for implementing main alkyl method for transformation and organic compound building-up reactions.
The catalytic composition that comprises material of the present invention advantageously is applied to following reaction: isomerization, transalkylation and disproportionation, alkylation and take off alkyl, hydration and dehydration, oligomeric and polymerization, cyclisation, aromizing, cracking is reformed, hydrogenation and dehydrogenation, oxidation, halogenation, hydrocracking, hydrocracking, hydrotreatment, the catalysis of hydrogenating desulfurization and hydrogenation denitration and oxynitride is eliminated, and wherein said reaction relates to and contains saturated and aliphatic unsaturated hydrocarbon, aromatic hydrocarbons, the organic compound of oxidation of organic compounds and nitrogenous and/or sulphur and the raw material that contains the organic compound of other functional group.
Below with embodiment the present invention is described.
Embodiment 1 (invention): the preparation of central hole structure aluminosilicate material with high aluminium content of Si/Al mol ratio=0.5.
The aluminum chloride of 3.38g is joined in the solution of the ctab surface promoting agent that contains 30g ethanol, 13.6ml water, 0.036ml HCl and 1.4g.One-piece construction is stirred at ambient temperature, till aluminum precursor dissolves fully.Add the tetraethyl orthosilicate (TEOS) of 1.45g then.After stirring 10 minutes at ambient temperature, one-piece construction is transported to the spray chamber of aerosol dispenser, this solution as mentioned above under the effect of the carrier gas of introducing with pressure (P=1.5 crust) (dry air) with the form spraying of small droplet.According in the schedule of operation described in the above specification sheets with droplet drying.The temperature of drying oven is set at 350 ℃.The powder of collecting was calcined 5 hours at T=550 ℃ in air then.Solid characterizes with little angle DRX (Fig. 1), nitrogen volumetry (Fig. 2, the PO that represents on X-coordinate amount is a saturation vapour pressure), TEM (Fig. 3), SEM and ICP.Tem analysis shows that final material has the peculiar orderly mesoporosity of vermicular texture.The nitrogen volumetry has obtained S
BET=780m
2The specific surface area of the final material of/g and the median pore diameter of φ=2.5nm.Little angle DRX analyzes and has shown the peak related with angle 2 θ=2.2.Bragg equation formula d*sin (1.1)=1.5406 can calculate the correlation distance d between the hole of central hole structure matrix, or d=4.0nm.Therefore the thickness of the wall of the central hole structure matrix by e=d-φ definition be e=1.5nm.Icp analysis provides and has equaled 0.5 Si/Al mol ratio.The SEM block of the substantially spherical particle of Huo Deing indication like this, these particles have the diameter of 50-700nm, and these particulate size-grade distribution concentrate on about 300nm.
Embodiment 2 (invention): the preparation of central hole structure aluminosilicate material with high aluminium content of Si/Al mol ratio=0.9.
The aluminum chloride of 2.65g is joined in the solution of the tensio-active agent P123 that contains 30g ethanol, 13.8ml water, 0.036ml HCl and 1.4g.This one-piece construction is stirred at ambient temperature, till aluminum precursor dissolves fully.Add the tetraethyl orthosilicate (TEOS) of 2g then.After stirring 18 hours at ambient temperature, this one-piece construction is transported to the spray chamber of aerosol dispenser, this solution as mentioned above under the effect of the carrier gas of introducing with pressure (P=1.5 crust) (dry air) with the form spraying of small droplet.According in the schedule of operation described in the above specification sheets with droplet drying.The temperature of drying oven is set at 350 ℃.The powder of collecting was calcined 5 hours at T=550 ℃ in air then.Solid characterizes with little angle DRX (Fig. 4), nitrogen volumetry (Fig. 5, the PO that represents on X-coordinate amount is a saturation vapour pressure), TEM (Fig. 6), SEM and ICP.Tem analysis shows that final material has the peculiar orderly mesoporosity of vermicular texture.The nitrogen volumetry has obtained S
BET=180m
2The specific surface area of the final material of/g and the median pore diameter of 5.6nm.Little angle DRX analyzes and has shown the peak related with angle 2 θ=0.64.Bragg equation formula 2d*sin (0.32)=1.5406 can calculate the correlation distance d between the hole of central hole structure matrix, or d=13.1nm.Therefore the thickness of the wall of the central hole structure matrix by e=d-φ definition be e=7.5nm.Icp analysis provides and has equaled 0.9 Si/Al mol ratio.The SEM block of the substantially spherical particle of Huo Deing indication like this, these particles have the diameter of 50-700nm, and these particulate size-grade distribution concentrate on about 300nm.
Embodiment 3 (invention): be included in the preparation of the central hole structure aluminosilicate material with high aluminium content of ZSM-5 (MFI) the type zeolite nanocrystal of holding back in the central hole structure alumo silicate matrix (mol ratio Si/Al=0.9) (mol ratio Si/Al=100, the 10wt% of final material).
Three aluminium secondary butylates of 0.14g are joined in the solution of the NaOH soda ash that contains 3.5ml TPAOH (TPAOH), 0.01g and 4.3ml water.Behind pure al dissolution, add the tetraethyl orthosilicate (TEOS) of 6g.This solution was stirred 5 hours at ambient temperature, then T=95 ℃ of following hot-pressing processing 12 hours.The white solution that is obtained contains the 135nmZSM-5 nanocrystal.With this solution 20, under the 000rpm centrifugal 30 minutes.With the solid redispersion in water, and then in 20, under the 000rpm centrifugal 30 minutes.This washing is carried out 2 times.Nanocrystal has formed gel, 60 ℃ one night of baking oven inner drying.By ultrasonic agitation 24 hours, with these crystal redispersion of 0.461mg in containing 30g ethanol, 13.8ml water, 2g TEOS, 2.65g AlCl
3, 6H
2In the solution of the P123 tensio-active agent of O, 0.036ml HCl and 1.4g.This one-piece construction is transported to the spray chamber of aerosol dispenser, this solution as mentioned above under the effect of the carrier gas of introducing with pressure (P=1.5 crust) (dry air) with the form spraying of small droplet.According in the schedule of operation described in the above specification sheets with droplet drying.The temperature of drying oven is set at 350 ℃.The powder of collecting was calcined 5 hours at T=550 ℃ in air then.Solid characterizes with little angle DRX (Fig. 7) and big angle DRX (Fig. 8), nitrogen volumetry (Fig. 9), TEM (Figure 10), SEM and ICP.Tem analysis shows that final material is made up of the ZSM-5 zeolite nanocrystal of holding back in the alumo silicate matrix with the peculiar orderly mesoporosity of vermicular texture.The nitrogen volumetry has obtained S
BET=310m
2The peculiar median pore diameter of aluminosilicate central hole structure matrix of the specific surface area of the final material of/g and φ=5.6nm.Big angle DRX analyzes and has obtained the distinctive diffractogram of ZSM-5 zeolite (the about 0.55nm of pore size).Little angle DRX analyzes and has shown the related peak relevant with the vermiform symmetry of central hole structure matrix.The Bragg equation formula provides 2d*sin (0.32)=1.5406, or d=13.1nm.Therefore the thickness of the amorphous wall of the aluminosilicate central hole structure matrix by e=d-φ definition be e=7.5nm.Icp analysis provides and has equaled 0.9 Si/Al mol ratio.The SEM block of the substantially spherical particle of Huo Deing indication like this, these particles have the diameter of 50-700nm, and these particulate size-grade distribution concentrate on about 300nm.
Claims (14)
1. central hole structure formed material, it is made up of at least two kinds of substantially spherical particles, described each particle comprises the central hole structure matrix based on aluminum oxide, described matrix has the aperture of 1.5-30nm and accounts for the above alumina content of 46wt% of described matrix, and having thickness is the amorphous wall of 1-30nm, and wherein said substantially spherical particle has the maximum diameter of 10 μ m.
2. material according to claim 1, wherein said central hole structure matrix based on aluminum oxide comprises silicon oxide.
3. material according to claim 2, wherein said central hole structure matrix have strict with 1 Si/Al mol ratio.
4. according to each described material of claim 1-3, wherein said central hole structure matrix has cubes, vermiform, cholesteric, lamelliform, co-continuous or hexagonal structure.
5. according to each described material of claim 1-3, wherein this material has 100-1200m
2The specific surface area of/g.
6. according to each described material of claim 1-3, wherein said each spheroidal particle comprises that the aperture is the zeolite nanocrystal of 0.2-2nm.
7. material according to claim 6, wherein said zeolite nanocrystal comprise the zeolite at least a MFI of being selected from, BEA, FAU and the LTA structure-type zeolite.
8. material according to claim 6, wherein said zeolite nanocrystal comprise at least a total silicon stone type zeolite.
9. material according to claim 6, wherein said zeolite nanocrystal comprises at least a zeolite that contains silicon and aluminium.
10. preparation comprises according to the method for each described central hole structure formed material of claim 1-9: a) mix at least a tensio-active agent, at least a aluminum precursor and optional at least a silica precursor in solution; B) solution that obtains in the step a) is carried out aerosol spray, form the spherical droplets that diameter is less than or equal to 200 μ m; C) dry described drop; And d) removes described tensio-active agent, obtain the central hole structure formed material.
11. the method for preparing the central hole structure formed material according to claim 10 comprises:
a
0) synthetic maximum nano-scale equals the zeolite nanocrystal of 300nm in the presence of at least a structurising agent, is scattered in wherein colloidal solution to obtain described nanocrystal; A ') in solution, mixes at least a tensio-active agent, at least a aluminum precursor, optional at least a silica precursor and at least a according to a
0) colloidal solution that obtains; B ') with step a ') in the solution that obtains carry out aerosol spray, form the spherical droplets that diameter is less than or equal to 200 μ m; C ') dry described drop; And d ') removes described tensio-active agent and described structurising agent, obtain central hole structure/zeolite mixing material.
12. the method for preparing the central hole structure formed material according to claim 10 comprises: a ") in solution, mix at least a tensio-active agent, at least a aluminum precursor, optional at least a silica precursor and be scattered in zeolite crystal in the described solution with the form that maximum nano-scale equals the nanocrystal of 300nm; B ") with step a ") in the solution that obtains carry out aerosol spray, form the spherical droplets that diameter is less than or equal to 200 μ m; C ") dry described drop; And d ") remove described at least tensio-active agent to obtain central hole structure/zeolite mixing material.
13. comprise according to claim 1-9 each the central hole structure formed material or according to the sorbent material of the central hole structure formed material of each preparation of claim 10-12.
14. comprise according to claim 1-9 each the central hole structure formed material or according to the catalyzer of the central hole structure formed material of each preparation of claim 10-12.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0505678A FR2886637B1 (en) | 2005-06-02 | 2005-06-02 | MESOSTRUCTURE MATERIAL WITH HIGH ALUMINUM CONTENT |
| FR0505678 | 2005-06-02 | ||
| PCT/FR2006/001112 WO2006128989A1 (en) | 2005-06-02 | 2006-05-17 | Mesostructured material with high aluminum content |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101189187A CN101189187A (en) | 2008-05-28 |
| CN101189187B true CN101189187B (en) | 2011-03-30 |
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ID=36129087
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| CN2006800192931A Expired - Fee Related CN101189187B (en) | 2005-06-02 | 2006-05-17 | Mesostructured materials with high aluminum content |
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|---|---|
| US (1) | US7807598B2 (en) |
| EP (1) | EP1910226B1 (en) |
| JP (1) | JP5150485B2 (en) |
| CN (1) | CN101189187B (en) |
| DE (1) | DE602006008312D1 (en) |
| FR (1) | FR2886637B1 (en) |
| WO (1) | WO2006128989A1 (en) |
| ZA (1) | ZA200708050B (en) |
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| FR2886636B1 (en) * | 2005-06-02 | 2007-08-03 | Inst Francais Du Petrole | INORGANIC MATERIAL HAVING METALLIC NANOPARTICLES TRAPPED IN A MESOSTRUCTURED MATRIX |
| FR2920757B1 (en) * | 2007-09-07 | 2009-11-13 | Inst Francais Du Petrole | CRYSTALLIZED MATERIAL COMPRISING SILICON HIERARCHISED AND ORGANIZED POROSITY |
| FR2920756B1 (en) * | 2007-09-07 | 2010-08-20 | Inst Francais Du Petrole | AMORPHOUS MATERIAL COMPRISING HIERARCHISED AND ORGANIC POROSITY SILICON |
| FR2929265B1 (en) * | 2008-03-31 | 2016-04-15 | Inst Francais Du Petrole | MATERIAL ALUMINOSILICATE MESOSTRUCTURE FORM OF SPHERICAL PARTICLES OF SPECIFIC SIZE |
| FR2929264B1 (en) | 2008-03-31 | 2010-03-19 | Inst Francais Du Petrole | INORGANIC MATERIAL FORM OF SPHERICAL PARTICLES OF SPECIFIC SIZE AND HAVING METALLIC NANOPARTICLES TRAPPED IN A MESOSTRUCTURED MATRIX |
| FR2929266B1 (en) | 2008-03-31 | 2010-03-19 | Inst Francais Du Petrole | MESOSTRUCTURE MATERIAL WITH A HIGH ALUMINUM CONTENT AND CONSISTING OF SPHERICAL PARTICLES OF A SPECIFIC SIZE |
| FR2931708B1 (en) * | 2008-05-28 | 2014-03-14 | Inst Francais Du Petrole | CATALYST BASED ON CRYSTALLIZED MATERIAL WITH HIERARCHISED AND ORGANIZED POROSITY AND USE IN OLIGOMERIZATION OF LIGHT OLEFINS |
| FR2931706B1 (en) * | 2008-05-28 | 2010-12-24 | Inst Francais Du Petrole | CATALYST BASED ON CRYSTALLIZED MATERIAL COMPRISING HIERARCHISED AND ORGANIZED POROSITY SILICON AND IMPROVED PROCESS FOR TREATING HYDROCARBON LOADS |
| FR2931834B1 (en) * | 2008-05-28 | 2010-07-30 | Inst Francais Du Petrole | PROCESS FOR THE PRODUCTION OF MEDIUM DISTILLATES BY HYDROCRACKING FISCHER-TROPSCH-LIKE CHARGES WITH A CATALYST BASED ON CRYSTALLIZED MATERIAL |
| FR2931705B1 (en) * | 2008-05-28 | 2010-09-03 | Inst Francais Du Petrole | CATALYST BASED ON AMORPHOUS MATERIAL COMPRISING HIERARCHISED AND ORGANIZED POROSITY SILICON AND IMPROVED PROCESS FOR TREATING HYDROCARBON LOADS |
| FR2931818B1 (en) * | 2008-05-28 | 2012-11-30 | Inst Francais Du Petrole | METHOD FOR OLIGOMERIZING LIGHT OLEFINS USING A CATALYST BASED ON AMORPHOUS MATERIAL WITH HIERARCHISED AND ORGANIZED POROSITY |
| FR2931833B1 (en) * | 2008-05-28 | 2011-06-10 | Inst Francais Du Petrole | PROCESS FOR THE PRODUCTION OF MEDIUM DISTILLATES BY HYDROCRACKING FISCHER-TROPSCH PROCESS CHARGES WITH A CATALYST BASED ON AMORPHOUS MATERIAL |
| FR2933088B1 (en) * | 2008-06-27 | 2010-08-20 | Inst Francais Du Petrole | PROCESS FOR PREPARING CONTROLLED MESOPOROSITY ALUMINA |
| FR2969511B1 (en) * | 2010-12-22 | 2012-12-28 | IFP Energies Nouvelles | SPHERICAL MATERIAL COMPRISING METALLIC NANOPARTICLES TRAPPED IN A MESOSTRUCTURED OXIDE MATRIX AND ITS USE AS CATALYST IN REFINING PROCESSES |
| FR2969513B1 (en) | 2010-12-22 | 2013-04-12 | IFP Energies Nouvelles | PROCESS FOR THE PREPARATION OF A SPHERICAL MATERIAL HIERARCHISED POROSITY COMPRISING METALLIC PARTICLES PIEGEES IN A MESOSTRUCTURED MATRIX |
| US8852326B2 (en) | 2011-03-07 | 2014-10-07 | Exxonmobil Research And Engineering Company | Aggregates of small particles of synthetic faujasite zeolite |
| US8882993B2 (en) | 2011-03-07 | 2014-11-11 | Exxonmobil Research And Engineering Company | Stabilized aggregates of small crystallites of zeolite Y |
| US8778171B2 (en) | 2011-07-27 | 2014-07-15 | Exxonmobil Research And Engineering Company | Hydrocracking catalysts containing stabilized aggregates of small crystallites of zeolite Y associated hydrocarbon conversion processes |
| US8778824B2 (en) | 2011-03-07 | 2014-07-15 | Exxonmobil Research And Engineering Company | Aggregates of small crystallites of zeolite Y |
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Also Published As
| Publication number | Publication date |
|---|---|
| ZA200708050B (en) | 2009-01-28 |
| FR2886637B1 (en) | 2007-08-03 |
| CN101189187A (en) | 2008-05-28 |
| JP2008542178A (en) | 2008-11-27 |
| DE602006008312D1 (en) | 2009-09-17 |
| EP1910226B1 (en) | 2009-08-05 |
| JP5150485B2 (en) | 2013-02-20 |
| US20090029847A1 (en) | 2009-01-29 |
| US7807598B2 (en) | 2010-10-05 |
| WO2006128989A1 (en) | 2006-12-07 |
| FR2886637A1 (en) | 2006-12-08 |
| EP1910226A1 (en) | 2008-04-16 |
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